Aminoalkyl-sulphonic acids and process of preparing them



' idly and completely. a

Patented Feb. 22, 1938 UNITED STATES PAT N OFFICE AMINOALKYL-SULPHONICACIDS AND PROCESS OF PREPARING THEM Otto Nicodemus and Walter Schmidt,Frankforton-the-Main-Hochst, Germany, assignors to General AnilineWorks, Inc., New York, N. Y., a. corporation of Delaware N 0 Drawing.

Application October 23, 1935, Se-- rial No. 46,440. In Germany October26, 1934 4 Claims.

relates to aminoalkyla process of preparing wherein X stands for thebasic radical of the salt of the disulphonic acid,

Rrepresents the sameordifierent alkyl residues or substitution productsthereof,

R1 and R2 stand for hydrogen, alkyl, aralkyl,

or aryl groups or the structure of a ring system as, for instance, inthe case of piperidine, morpholine, piperazine, pyrrolidineorsubstitution products thereof, or

R1 stands for hydrogen-and R2 for OH or NH:

' (which may be substituted by alkyl or aryi radicals).

As bases containing nitrogen there may also be used, besides ammonia,for instance, hydroxylamine, hydrazine or a substituted hydrazine, suchas phenylhydrazine or methylhydrazine; moreover, primary and secondaryamines of the allphatic, aliphatic-aromatic and aromatic series orsubstitution products thereof. Theremay be named, for instance,methylamine, butylamine, dodecylamine, cyclohexylamine, benzylamine,piperidine, piperazine, pyrrolidine, aniline, diethylamine,ethanolamine, ethylenediamine, chloraniline, and so on. Asether-disulphonic acids there may be named:diethyl-ether-beta,betadisulphonic acid, dipropylether-disulphonic acidand dibutylether-disulphonic acid; the acids may be obtained in knownmanner from sodium sulphite and the correspondingdihalogen-dialkyiethers.

The reaction between the salts of diaikyletherdisulphonic acids and thebases containing nitrogen commences even at a temperature below 100 C.;at a higher temperature it proceeds rap- The addition of a fixed alkalimay have a favorable influence on the reaction.

The invention provides an entirely new process being ethyl in case R2.thereto, the parts C. to 242 for obtaining easily theaminoalkyl-sulphonic acids and their homologues and substitutionproducts. These bodies are of industrial value, especially for themanufacture of auxiliary agents for the textile industry. Some of themcould not hitherto be prepared or could be prepared only with greatdiflicultyl 7 Those among the aminoalkyl-sulphonic acids which are newproducts are characterized by the following general formula:

80;.alkali metal 1 wherein R, R1 and R2 stand for alkyl. or 'R1 standsfor hydrogen and R2 for hydrogen, OH, NHz, alkyl, aryl, NH-alkyl orNH-aryl, R. not

is hydrogen or methyl.

The following examples serve to illustrate the invention, but'they arenot intended to limit it being by weight: I

1) 400 parts of sodium diethylether-disulphonate containing 28 per cent.of sodium chlo-' ride, obtainable by causingbeta,bet-a-dichiorodiethylether to react completely with sodiumsulphite, are heated for 5 hours at 230 C. to 232 C. under a pressure of66 to 73 atmospheres above atmospheric pressure inan autoclaveprovidedwith a stirrer with 1100 parts of an aqueous methylaminesolution of 36 per cent. strength in the presence of 30 parts of acaustic soda solution of 33 per cent. strength. After recovering theexcess of methylamine, the solution yields on evaporation'to dryness 410parts of a product containing 56 per cent. of the sodium salt of trogenof 5.72-per cent. The product is treated with concentrated hydrochloricacid and the residue or the hydrochloric acid solution is recrystallizedfrom dilute alcohol. The purified product thus obtained is identified asmethyltaurine by its melting point which lies at 245 C. and is the sameas that of a mixture of the product with pure methyl-taurine.

(2) 200 parts of technical sodium diethyletherdisulphonate are' heatedfor 5 hours at 239 C. under a pressure of 31 to 33-atmospheres aboveatmospheric pressure with 200 parts of water, 20 parts of a concentratedcaustic soda solution and 500 parts of aniline. The excess of aniline isexpelled by steam-distillation and the aqueous solution is evaporated todryness.

There are obtained 291 partsof a product containing 56 per cent. of thesodium salt of phenyltaurine.

(3) 200 parts of technical sodium diethyletherdisulphonate are heatedfor 4 /2 hours at 239 C. to 241 C. under a pressure of to 54 atmospheresabove atmospheric pressure with 200 parts of water, 20 parts of aconcentrated caustic soda solution and 400 parts of an aqueousdimethylamine solution of 49 per cent. strength. After distillation ofthe excess of dimethylamine and evaporation of the reaction solutionthere are obtained 232 parts of a product which contains the sodium saltof dimethyltaurine in a quantity representing a good yield.

(4) 95 parts of a technical salt containing65% of sodiumdiethylether-alpha,alpha'-disulphonate, obtainable by causingalpha,alpha-dichlorodiethylether to react with sodium sulphite, areheated with 300 parts of a methylamine solution of 40 per cent. strengthfor 3 /2 hours at 220 C. under a pressure of 54 to 58 atmospheres aboveatmospheric pressure in an autoclave after addition of 5 parts ofcaustic soda solution of 33% strength. The reaction product contains onevaporation to dryness 2.6% of nitrogen which corresponds with a contentof 29.9% of sodium alpha-methyl-amino-ethanesulphonate.

(5) 45 parts of sodium ethylisopropyletherbeta,beta-disulphonate of 66%strength (obtainable from beta,beta'-dichloroethyl-isopropylether) areheated for 4 hours at 215 C. to 220 C. under a pressure of 32 to 34atmospheres above atmospheric pressure with 350 parts of an aqueoussolution of butylamine of 80% strength. The

solution is evaporated and the residue contains a mixture of sodiumbutylamino-ethane-sulphonate and sodium butylamino-isopropanesulphonatewith a content of nitrogen of 3.94 to 4.12%.

(6), 31 parts of sodium ethylisobutyletherbeta,beta'-disulphonate of 65%strength are heated for 5 hours at 218 C. to 223 C. under a pressure of42 to 49 atmospheres above atmospheric pressure with 200 parts of amethylamine solution of 40% strength and 2 parts of caustic sodasolution. The solution of the reaction yields on evaporation a mixtureof sodium methylaminoethanesulphonate and sodiummethylamino-isobutanesulphonate, the analysis of which shows a contentof 2.27% of nitrogen.

('7) 200 parts of a sodium diethylether-beta, strength are heated for 4%hours at 220 C. to 230 C. under a pres sure of 32 to 45 atmospheresabove atmospheric pressure with 600 parts of concentrated aqueousammonia after addition of 10 parts of caustic soda solution.

After evaporation of the solution there are obtained 213 parts of amixture of taurine and ditaurine containing 21.2% of sodium taurine and33.7% of sodium ditaurine.

(8) 20 parts of sodium diethylether-beta,betadisulphonate of 70%strength are dissolved in water and heated, while stirring, to boilingfor 6 hours in a reflux apparatus after addition of 2 parts .of causticsoda solution with 30 parts of phenylhydrazine. After cooling, thephenylhydrazine in excess is extracted with ether and the aqueoussolution is evaporated to dryness. There are obtained 26 partscontaining 3.34 to 3.42% of nitrogen.

(9) 17 parts of hydroxylaminehydrochloride in parts of methylalcohol aremixed with 14 parts of sodium methylate whereupon the base is set freewith formation of heat. After addition of an aqueous solution of '10parts of sodium ethyletherdisulphonate the whole is slowly heated in anautoclave and kept at a temprature of 60 C. to 73 C. for 17 hours. Aftercooling, the solution of the reaction is evaporated to dryness in asteam bath; the residue contains 16.3% of sodiumhydroxylaminoethanesulphonate.

(10) 29 parts of sodium dimethyletherdisulphonate of 47% strength,obtainable by causing symmetrical dichlorodimethylether to react withsodium sulphite, are heated for 5 /2 hours at 198 C. to 205 C. in anautoclave under a pressure of 38 to 46 atmospheres above atmosphericpressure with 200 parts of an aqueous methylamine solution of 40%strength. The distillation of the methylamine is followed by completeevaporation; the residue contains 18.2% of sodiummethylaminomethanesulphonate.

We claim:

1. The processwhich comprises heating an alkali metal salt ofdiethylether-disulphonic acid with methylamine.

2. The process which comprises heating under raised pressure an alkalimetal salt of diethylether-beta,beta'-disulphonic acid with ammonia inthe presence of caustic soda solution.

3. The process which comprises heating an alkali metal salt ofdiethylether-disulphonic acid with aniline. 4. The process of preparingaminoalkyl-sulphonic acids which comprises heating alkali metal salts ofdialkylether-disulphonic acids with nitrogen-containing bases'which haveat. least one replaceable hydrogen atom attachedto the nitrogen atomselected from the group consisting of compounds of the general formulawherein R1 stands for a member of the group consisting of H, alkyl,aralkyl and aryland R2 stands for a member of the group consisting of H,OH, NHz', NH-alkyl, NH-aryl, alkyl, aralkyl and aryl.

OTTO NICODEMUS.

WALTER SCHMIDT.

